A gas chromatography-mass spectrometry instrument and a method for detecting decomposition products of mixed gas discharge

Abstract

The embodiment of the present application discloses a gas chromatography-mass spectrometry instrument and a detection method for decomposition products of mixed gas discharge. The sample quantification component is used to quantitatively control the sample gas and divide the sample gas into two paths, which are respectively sent into the first chromatographic column, the first channel and the second chromatographic column, the second channel; wherein, the first channel is a BID channel, and the BID channel is used to detect substances before the peak emergence time of the sample gas SF6, mainly including N2, O2, NF3, CF4, CH4, H2; wherein, the second channel is an MSD channel, and the MSD channel is used to detect substances after the peak emergence time of the sample gas SF6, mainly including SO2F2, SOF2, COS, SO2, N2O, C2F6, C3F8; the present invention can realize the calibration of the existing standard gas, and there are no interference peaks and impurities when detecting unknown samples; it is of great help to the detection of decomposition products of SF6 / N2 mixed gas, and lays a foundation for realizing equipment defect diagnosis through characteristic decomposition products.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of gas purification treatment, and in particular, to a gas chromatography-mass spectrometry instrument and a method for detecting decomposition products of a mixed gas discharge. Background Technique

[0002] SF6 gas is widely used in the power industry due to its good insulation performance and arc extinguishing performance. N2 has the advantages of little environmental pollution, low price, and stable chemical properties. In recent years, the mixed gas of N2 and SF6 has been widely used as a gas insulation medium in the power industry. Accurately detecting the decomposition products of SF6 / N2 mixed gas under different discharge conditions is of great significance for finding characteristic decomposition products, proposing defect diagnosis methods, and improving the operation stability of the power grid. At present, a gas chromatography-mass spectrometry instrument can be used to comprehensively detect the decomposition products. The gas chromatography-mass spectrometry instrument has both the advantages of mass spectrometry quantification and the advantages of chromatography qualitative analysis. Its working principle is: performing chromatographic separation on the product to be measured, separating different components in the mixture through a chromatographic column according to different physical and chemical properties; ionizing the components separated by chromatography through a mass spectrometer, and accurately determining their chemical components according to their mass-to-charge ratio.

[0003] The traditional detection of a gas chromatography-mass spectrometry instrument adopts a single-channel injection method, and there is only one chromatographic column to separate the mixture. Since the physical and chemical properties of the decomposition products of SF6 / N2 mixed gas discharge are similar, it is difficult to effectively distinguish all the products of generation using one chromatographic column, which easily leads to fewer peaks in the detected result spectrogram, and often the situation that large peaks contain small peaks, resulting in the inability to accurately determine all the products of generation. And due to the relatively large content of nitrogen in the SF6 / N2 mixed gas, the products of generation (such as CH4, NF3, CF4, O2, etc.) with properties similar to nitrogen cannot show obvious peaks, thus affecting the detection effect. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art or related technologies.

[0005] Therefore, in the first aspect of the present invention, a gas chromatography-mass spectrometry instrument is provided.

[0006] In the second aspect of the present invention, a method for detecting decomposition products of a mixed gas discharge is provided.

[0007] In view of this, according to the first aspect of the embodiments of the present application, a gas chromatography-mass spectrometry instrument is proposed, including:

[0008] A sample quantification component, which is used to quantitatively control the sample gas and divide the sample gas into two paths;

[0009] A first chromatographic column, which is connected to the sample quantification component;

[0010] A first channel, which is connected to the first chromatographic column. The first channel is a dielectric barrier discharge plasma detector channel and is used to detect substances before the peak time of the sample gas SF6.

[0011] A second chromatographic column, which is connected to the sample quantification assembly.

[0012] A second channel, which is connected to the second chromatographic column. The second channel is a mass spectrometry detector channel and is used to detect substances after the peak time of the sample gas SF6.

[0013] In a feasible implementation manner, the sample quantification assembly includes:

[0014] A ten-way valve, which has a first state and a second state and is connected to the first chromatographic column and the second chromatographic column.

[0015] A sample intake pipeline, which is connected to the ten-way valve.

[0016] A sample exhaust pipeline, which is connected to the ten-way valve.

[0017] A first quantitative loop, which is connected to the ten-way valve.

[0018] A second quantitative loop, which is connected to the ten-way valve.

[0019] A first carrier gas inlet, which is connected to the ten-way valve.

[0020] In a feasible implementation manner, when the ten-way valve is in the first state, the second valve inside the ten-way valve is connected to the third valve, the fourth valve is connected to the fifth valve, the sixth valve is connected to the seventh valve, the eighth valve is connected to the ninth valve, and the tenth valve is connected to the first valve;

[0021] When the ten-way valve is in the second state, the first valve inside the ten-way valve is connected to the second valve, the third valve is connected to the fourth valve, the fifth valve is connected to the sixth valve, the seventh valve is connected to the eighth valve, and the ninth valve is connected to the tenth valve;

[0022] The sample intake pipeline is connected to the second valve of the ten-way valve;

[0023] The sample exhaust pipeline is connected to the first valve of the ten-way valve;

[0024] One end of the first quantitative loop is connected to the seventh valve of the ten-way valve, and the other end of the first quantitative loop is connected to the tenth valve of the ten-way valve;

[0025] One end of the second quantitative loop communicates with the third valve of the ten-way valve, and the other end of the second quantitative loop communicates with the sixth valve of the ten-way valve;

[0026] The first chromatographic column communicates with the eighth valve of the ten-way valve, and the second chromatographic column communicates with the fourth valve of the ten-way valve;

[0027] The first carrier gas inlet communicates with the ninth valve of the ten-way valve;

[0028] The second carrier gas inlet is connected to the fifth valve of the ten-way valve.

[0029] In a feasible implementation manner, it further includes:

[0030] A shunt assembly, which is arranged between the first chromatographic column and the first channel. When SF6 in the sample gas reaches the peak emergence time, the shunt assembly introduces the sample gas into the first channel. When SF6 in the sample gas reaches the peak emergence time, the shunt assembly discharges the sample gas.

[0031] In a feasible implementation manner, the shunt assembly includes:

[0032] A six-way valve, which has a first state and a second state;

[0033] When the six-way valve is in the first state, the second valve inside the six-way valve communicates with the third valve, the fourth valve communicates with the fifth valve, and the sixth valve communicates with the first valve;

[0034] When the six-way valve is in the second state, the first valve inside the six-way valve communicates with the second valve, the third valve communicates with the fourth valve, and the sixth valve communicates with the first valve;

[0035] The sixth valve of the six-way valve communicates with the first chromatographic column, and the first valve of the six-way valve communicates with the first channel;

[0036] A third chromatographic column, which communicates with the first valve of the six-way valve and the third chromatographic column communicates with the second channel;

[0037] An exhaust port, which communicates with the fifth valve of the six-way valve.

[0038] In a feasible implementation manner, the sample quantification assembly further includes:

[0039] A shunt flow path, which is arranged between the sample quantification assembly and the second chromatographic column.

[0040] In a feasible implementation manner, the shunt assembly further includes:

[0041] A carrier gas circuit, one end of the carrier gas circuit is connected to the second valve of the six-way valve, and the other end of the carrier gas circuit is connected to the fourth valve of the six-way valve;

[0042] A third carrier gas inlet, the third carrier gas inlet is connected to the third valve of the six-way valve.

[0043] In a feasible implementation manner, the chromatographic column selected for the first chromatographic column is a Q column;

[0044] The chromatographic column selected for the second chromatographic column is a Q column and a CPCIL5 column;

[0045] The chromatographic column selected for the third chromatographic column is a 5A molecular sieve.

[0046] According to the second aspect of the embodiments of the present application, a method for detecting the decomposition products of a mixed gas discharge is proposed, which is applied to the gas chromatography-mass spectrometry instrument in any one of the above, and includes:

[0047] Introduce the decomposition products of the SF6 / N2 mixed gas into the sample quantification component. When no detection signal is sent to the sample quantification component, the ten-way valve in the sample quantification component is in the first state, and the SF6 / N2 mixed gas is directly discharged after being sent into the sample quantification component;

[0048] Send a detection signal to the sample quantification component, and the ten-way valve in the sample quantification component is switched from the first state to the second state;

[0049] The sample quantification component introduces the decomposition products of the SF6 / N2 mixed gas into the first chromatographic column and the second chromatographic column;

[0050] The decomposition products of the SF6 / N2 mixed gas enter the first channel through the first chromatographic column, and the first channel detects the substances before the peak time of SF6 in the mixed gas;

[0051] The decomposition products of the SF6 / N2 mixed gas enter the second channel through the second chromatographic column, and the second channel detects the substances after the peak time of SF6 in the mixed gas.

[0052] In a feasible implementation manner, it further includes:

[0053] A shunt component is arranged between the first chromatographic column and the first channel, and the shunt component is used to introduce the sample gas into the first channel or discharge it from the gas chromatography-mass spectrometry instrument;

[0054] When SF6 in the sample gas has not reached the peak position, the shunt component introduces the sample gas into the first channel;

[0055] After SF6 in the sample gas reaches the peak position, an electrical signal is sent to the shunt assembly, and the shunt assembly discharges the sample gas from the gas chromatography-mass spectrometry instrument.

[0056] Compared with the prior art, the present invention has at least the following beneficial effects: The present invention realizes dual-channel detection. Compared with the existing single-channel detection combined instrument, the present invention solves the problems that the peak emergence time of the above substances is not obvious and they are included in the peaks of other substances.

[0057] By modifying the gas chromatography-mass spectrometry instrument, the present invention increases the injection channel. Currently, it can realize dual-channel injection of the first channel BID channel and the second channel MSD channel, and uses the first chromatographic column and the second chromatographic column to separate the sample, avoiding the situation where the existing samples cannot be completely separated when detected by the existing single-channel combined instrument.

[0058] Currently, the present invention can calibrate the existing standard gas, and there are no interference peaks and impurities when detecting unknown samples. It is of great help to the detection of the decomposition products of the SF6 / N2 mixed gas, laying a foundation for realizing equipment defect diagnosis through characteristic decomposition products. Description of the Drawings

[0059] By reading the following detailed description of the preferred embodiments, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present application. Moreover, throughout the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0060] Figure 1 It is a flow path diagram of a gas chromatography-mass spectrometry instrument according to an embodiment provided by the present application;

[0061] Figure 2 It is a schematic flow chart of a method for detecting the decomposition products of a mixed gas discharge according to an embodiment provided by the present application;

[0062] Figure 3 It is a detection effect diagram of an existing single-channel detector;

[0063] Figure 4 It is another detection effect diagram of an existing single-channel detector;

[0064] Figure 5 It is a BID channel detection chromatogram of a gas chromatography-mass spectrometry instrument according to an embodiment provided by the present application;

[0065] Figure 6 It is a BID channel detection table of a gas chromatography-mass spectrometry instrument according to an embodiment provided by the present application;

[0066] Figure 7Chromatogram of calibration gas 1 of a chromatograph - mass spectrometer according to an embodiment provided by this application;

[0067] Figure 8 Chromatogram of calibration gas 2 of a chromatograph - mass spectrometer according to an embodiment provided by this application;

[0068] Figure 9 Chromatogram of calibration gas 3 of a chromatograph - mass spectrometer according to an embodiment provided by this application.

[0069] Among them, Figure 1 The corresponding relationship between the reference numerals and the component names in the figure is:

[0070] 100, sample quantification component; 200, first chromatographic column; 300, first channel; 400, second chromatographic column; 500, second channel; 600, shunt component;

[0071] 110, ten - way valve; 120, sample inlet pipeline; 130, sample exhaust pipeline; 140, first quantitative loop; 150, second quantitative loop; 160, first carrier gas inlet; 170, second carrier gas inlet; 180, shunt flow path;

[0072] 610, six - way valve; 620, third chromatographic column; 630, exhaust port; 640, carrier gas loop; 650, third carrier gas inlet. Detailed implementation manners

[0073] To better understand the above - mentioned technical solution, the technical solution of the embodiment of this application will be described in detail below through the drawings and specific embodiments. It should be understood that the specific features in the embodiments of this application and the embodiments are detailed descriptions of the technical solution of the embodiment of this application, rather than limitations on the technical solution of this application. Without conflict, the technical features in the embodiments of this application and the embodiments can be combined with each other.

[0074] Such as Figure 1As shown in the figure, a gas chromatography-mass spectrometry (GC-MS) instrument according to the first aspect of the embodiments of the present application includes: a sample quantification component 100 for quantitatively controlling a sample gas and dividing the sample gas into two paths; a first chromatographic column 200 connected to the sample quantification component 100; a first channel 300 connected to the first chromatographic column 200, where the first channel 300 is a dielectric barrier discharge plasma detector channel for detecting substances before the peak time of the sample gas SF6; a second chromatographic column 400 connected to the sample quantification component 100; and a second channel 500 connected to the second chromatographic column 400, where the second channel 500 is a mass spectrometry detector channel for detecting substances after the peak time of the sample gas SF6.

[0075] In this embodiment of the GC-MS instrument, the sample gas to be detected is the discharge decomposition product of an SF6 / N2 mixed gas.

[0076] The GC-MS instrument provided by the embodiments of the present application includes a sample quantification component 100, a first chromatographic column 200, a first channel 300, a second chromatographic column 400, and a second channel 500.

[0077] During use, the sample quantification component 100 is used to quantitatively control the sample gas and divide the sample gas into two paths, which are respectively sent to the first chromatographic column 200, the first channel 300 and the second chromatographic column 400, the second channel 500.

[0078] Among them, the first channel 300 is a dielectric barrier discharge plasma detector channel (hereinafter abbreviated as the BID channel), and the BID channel is used to detect substances before the peak time of the sample gas SF6, mainly including N2, O2, NF3, CF4, CH4, H2.

[0079] Among them, the second channel 500 is a mass spectrometry detector channel (hereinafter abbreviated as the MSD channel), and the MSD channel is used to detect substances after the peak time of the sample gas SF6, mainly including SO2F2, SOF2, COS, SO2, N2O, C2F6, C3F8.

[0080] Furthermore, the present invention realizes dual-channel detection. Compared with the existing single-channel detection combined instrument, the present invention solves the problems that the peak times of the above substances are not obvious and are included in the peaks of other substances.

[0081] Through the transformation of the chromatograph-mass spectrometer, the present invention adds a sample injection channel. Currently, dual-channel injection can be achieved, namely, the 300BID channel of the first channel and the 500MSD channel of the second channel. The first chromatographic column 200 and the second chromatographic column 400 are used to separate the samples, avoiding the situation that the existing samples cannot be completely separated when detected by the existing single-channel combined instrument.

[0082] Currently, the present invention can calibrate the existing standard gas, and there are no interference peaks and impurities when detecting unknown samples. It is of great help to the detection of the decomposition products of the SF6 / N2 mixed gas, laying a foundation for realizing the diagnosis of equipment defects through characteristic decomposition products.

[0083] As Figure 1 shown, the sample quantification assembly 100 includes: a ten-way valve 110, which has a first state and a second state, and the ten-way valve 110 is connected to the first chromatographic column 200 and the second chromatographic column 400; a sample inlet pipeline 120, which is connected to the ten-way valve 110; a sample exhaust pipeline 130, which is connected to the ten-way valve 110; a first quantitative loop 140, which is connected to the ten-way valve 110; a second quantitative loop 150, which is connected to the ten-way valve 110; a first carrier gas inlet 160, which is connected to the ten-way valve 110.

[0084] As Figure 1 shown, when the ten-way valve 110 is in the first state, the second valve inside the ten-way valve 110 is connected to the third valve, the fourth valve is connected to the fifth valve, the sixth valve is connected to the seventh valve, the eighth valve is connected to the ninth valve, and the tenth valve is connected to the first valve; when the ten-way valve 110 is in the second state, the first valve inside the ten-way valve 110 is connected to the second valve, the third valve is connected to the fourth valve, the fifth valve is connected to the sixth valve, the seventh valve is connected to the eighth valve, and the ninth valve is connected to the tenth valve; the sample inlet pipeline 120 is connected to the second valve of the ten-way valve 110; the sample exhaust pipeline 130 is connected to the first valve of the ten-way valve 110; one end of the first quantitative loop 140 is connected to the seventh valve of the ten-way valve 110, and the other end of the first quantitative loop 140 is connected to the tenth valve of the ten-way valve 110; one end of the second quantitative loop 150 is connected to the third valve of the ten-way valve 110, and the other end of the second quantitative loop 150 is connected to the sixth valve of the ten-way valve 110; the first chromatographic column 200 is connected to the eighth valve of the ten-way valve 110, and the second chromatographic column 400 is connected to the fourth valve of the ten-way valve 110; the first carrier gas inlet 160 is connected to the ninth valve of the ten-way valve 110; the second carrier gas inlet 170 is connected to the fifth valve of the ten-way valve 110.

[0085] In this technical solution, the sample quantification component 100 includes a ten-way valve 110, a sample intake pipeline 120, a sample exhaust pipeline 130, a first quantitative loop 140, a second quantitative loop 150, and a first carrier gas inlet 160.

[0086] Among them, the ten-way valve 110 has ten valve ports. In the present invention, they are sequentially named as the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the seventh valve, the eighth valve, the ninth valve, and the tenth valve of the ten-way valve 110.

[0087] As Figure 1 shown, in the ten-way valve 110 in the figure, the valve port marked 1 is the first valve of the ten-way valve 110, the valve port marked 2 is the second valve of the ten-way valve 110, the valve port marked 3 is the third valve of the ten-way valve 110, the valve port marked 4 is the fourth valve of the ten-way valve 110, the valve port marked 5 is the fifth valve of the ten-way valve 110, the valve port marked 6 is the sixth valve of the ten-way valve 110, the valve port marked 7 is the seventh valve of the ten-way valve 110, the valve port marked 8 is the eighth valve of the ten-way valve 110, the valve port marked 9 is the ninth valve of the ten-way valve 110, and the valve port marked 10 is the tenth valve of the ten-way valve 110.

[0088] Among them, the sample intake pipeline 120 is connected to the second valve of the ten-way valve 110, and the sample exhaust pipeline 130 is connected to the first valve of the ten-way valve 110.

[0089] Among them, the first quantitative loop 140 is connected between the seventh valve and the tenth valve of the ten-way valve 110, and the second quantitative loop 150 is connected between the third valve and the sixth valve of the ten-way valve 110.

[0090] Among them, the ten-way valve 110 has a first state and a second state. When the ten-way valve 110 is in the first state, the second valve of the ten-way valve 110 is connected to the third valve, the fourth valve is connected to the fifth valve, the sixth valve is connected to the seventh valve, the eighth valve is connected to the ninth valve, and the tenth valve is connected to the first valve; when the ten-way valve 110 is in the second state, the first valve of the ten-way valve 110 is connected to the second valve, the third valve is connected to the fourth valve, the fifth valve is connected to the sixth valve, the seventh valve is connected to the eighth valve, and the ninth valve is connected to the tenth valve.

[0091] Among them, the first carrier gas inlet 160 is connected to the fifth valve of the ten-way valve 110.

[0092] During use, when no detection signal is sent to the ten-way valve 110, the ten-way valve 110 is in the first state. When the ten-way valve 110 is in the first state, the gas flow path of the sample quantification assembly 100 is as follows: the sample inlet pipe 120 supplies sample gas into the second valve of the ten-way valve 110. The sample gas enters the third valve from the second valve, passes through the second quantification loop 150 from the third valve to enter the sixth valve, enters the seventh valve from the sixth valve, passes through the first quantification loop 140 from the seventh valve to enter the tenth valve, and the sample gas is discharged from the tenth valve through the sample exhaust pipe 130.

[0093] After a detection signal is sent to the ten-way valve 110, the ten-way valve 110 switches from the first state to the second state.

[0094] At this time, the sample inlet pipe 120 sends sample gas into the second valve of the ten-way valve. The sample gas flows into the first valve from the second valve and is discharged through the sample exhaust pipe 130.

[0095] The first carrier gas inlet 160 sends carrier gas into the ten-way valve 110 through the ninth valve of the ten-way valve 110. The carrier gas is sent into the tenth valve from the ninth valve, enters the first quantification loop 140 from the tenth valve. The carrier gas pushes the sample gas in the first quantification loop 140 to enter the seventh valve from the first quantification loop 140, enters the eighth valve from the seventh valve, and enters the first chromatographic column 200 from the eighth valve, thereby realizing the feeding of a quantified sample gas into the first chromatographic column 200 and the first channel 300.

[0096] The second carrier gas inlet 170 sends carrier gas into the ten-way valve 110 through the fifth valve of the ten-way valve 110. The carrier gas flows into the sixth valve from the fifth valve, enters the second quantification loop 150 from the sixth valve. The carrier gas pushes the sample gas in the second quantification loop 150 to enter the third valve and sends the sample gas into the second chromatographic column 400 and the second channel 500 through the third valve.

[0097] Through the above gas flow path, when performing detection, the sample gas in the first quantification loop 140 is sent into the first chromatographic column 200 and the first channel 300, and the sample gas in the second quantification loop 150 is sent into the second chromatographic column 400 and the second channel 500, thereby realizing dual-channel detection.

[0098] As Figure 1 shown, the gas chromatography-mass spectrometry instrument further includes: a shunt assembly 600. The shunt assembly 600 is arranged between the first chromatographic column 200 and the first channel 300. Before the SF6 in the sample gas reaches the peak time, the shunt assembly 600 introduces the sample gas into the first channel 300. After the SF6 in the sample gas reaches the peak time, the shunt assembly 600 discharges the sample gas.

[0099] In this technical solution, the chromatograph-mass spectrometer further includes a shunt assembly 600. In the existing single-channel detector, a 5A molecular sieve chromatographic column is usually used for the chromatographic column. Since the SF6 decomposition products contain products with strong corrosiveness, the 5A molecular sieve chromatographic column will be corroded, resulting in poor separation effect of the chromatographic column during multiple injections and inaccurate detection results. To solve this problem, a shunt assembly 600 is provided between the first chromatographic column 200 and the first channel 300. Before the SF6 in the sample gas reaches the peak position, the shunt assembly 600 introduces the sample gas into the first channel 300, so that the first channel 300 can detect the sample gas. After the SF6 in the sample gas reaches the peak position, the shunt assembly 600 can discharge the sample gas from the loop of the combined instrument, thus avoiding the decomposition products of SF6 from corroding the chromatographic column in the shunt assembly 600.

[0100] As Figure 1 shown, the shunt assembly 600 includes: a six-way valve 610, which has a first state and a second state; when the six-way valve 610 is in the first state, the second valve inside the six-way valve 610 is connected to the third valve, the fourth valve is connected to the fifth valve, and the sixth valve is connected to the first valve; when the six-way valve 610 is in the second state, the first valve inside the six-way valve 610 is connected to the second valve, the third valve is connected to the fourth valve, and the sixth valve is connected to the first valve; a third chromatographic column 620, which is connected to the first valve of the six-way valve 610 and is connected to the second channel 500; an exhaust port 630, which is connected to the fifth valve.

[0101] As Figure 1 shown, in the six-way valve 610 in the figure, the valve port marked 1 is the first valve of the six-way valve 610, the valve port marked 2 is the second valve of the six-way valve 610, the valve port marked 3 is the third valve of the six-way valve 610, the valve port marked 4 is the fourth valve of the six-way valve 610, the valve port marked 5 is the fifth valve of the six-way valve 610, and the valve port marked 6 is the sixth valve of the six-way valve 610.

[0102] In this technical solution, the shunt assembly 600 includes a six-way valve 610, a third chromatographic column 620, and an exhaust port 630.

[0103] Among them, the six-way valve 610 has six valve ports, and these six valve ports are respectively named the first valve, the second valve, the third valve, the fourth valve, the fifth valve, and the sixth valve of the six-way valve 610.

[0104] Among them, the six-way valve 610 has a first state and a second state. When the sample gas is before the peak time of SF6, an electrical signal is used to make the six-way valve 610 in the first state. When the six-way valve 610 is in the first state, the second valve inside the six-way valve is connected to the third valve, the fourth valve is connected to the fifth valve, and the sixth valve is connected to the first valve.

[0105] In this state, the sample gas flows from the first chromatographic column 200 to the sixth valve of the six-way valve 610, from the sixth valve to the first valve, and from the first valve to the first channel 300.

[0106] Among them, the shunt assembly 600 further includes a third chromatographic column 620, and the third chromatographic column 620 is disposed between the first channel 300 and the first valve of the six-way valve 610.

[0107] After the sample gas reaches the peak emergence time of SF6, the six-way valve 610 is switched from the first state to the second state by an electrical signal. When the six-way valve 610 is in the second state, the first valve in the six-way valve 610 is connected to the second valve, the third valve is connected to the fourth valve, and the fifth valve is connected to the sixth valve.

[0108] In this state, the sample gas flows from the first chromatographic column 200 to the sixth valve of the six-way valve 610, the sample gas flows from the sixth valve to the fifth valve, and is discharged from the exhaust port 630 connected to the fifth valve.

[0109] The present invention realizes, through the above structure, that before the sample gas SF6 reaches the peak emergence time, the sample gas is sent into the first channel 300 through the third chromatographic column 620, and after the sample gas SF6 reaches the peak emergence time, the sample gas is discharged, thereby effectively avoiding the decomposition products of SF6 from corroding the third chromatographic column 620.

[0110] As Figure 1 shown, the sample quantification assembly 100 further includes: a shunt flow path 180, and the shunt flow path 180 is disposed between the sample quantification assembly 100 and the second chromatographic column 400.

[0111] In this technical solution, a shunt flow path 180 is disposed between the sample quantification assembly 100 and the second chromatographic column 400. The shunt flow path 180 is used to control the concentration of the sample entering the instrument. When the concentration of the sample gas is high, the shunt flow path 180 adopts a split injection method to reduce the concentration of the sample gas entering the instrument.

[0112] This setting can avoid saturation caused by the sample concentration being too high and directly entering the second chromatographic column 400 and the second channel 500, and improve the stability of the present invention.

[0113] As Figure 1 shown, the shunt assembly 600 further includes: a carrier gas circuit 640, one end of the carrier gas circuit 640 is connected to the second valve of the six-way valve 610, and the other end of the carrier gas circuit 640 is connected to the fourth valve of the six-way valve 610; a third carrier gas inlet 650, and the third carrier gas inlet 650 is connected to the third valve of the six-way valve 610.

[0114] In this technical solution, the shunt assembly 600 further includes a carrier gas circuit 640 and a third carrier gas inlet 650. Among them, the carrier gas circuit 640 is connected to the second valve and the fourth valve of the six-way valve 610, and the third carrier gas inlet 650 is connected to the third valve of the six-way valve 610.

[0115] During use, when the six-way valve 610 is in the first state, the carrier gas enters the third valve of the six-way valve 610 from the third carrier gas inlet 650, enters the second valve from the third valve of the six-way valve 610, enters the carrier gas circuit 640 from the second valve, enters the fourth valve from the carrier gas circuit 640, enters the fifth valve from the fourth valve, and finally discharges from the exhaust port 630 connected to the fifth valve to exit the circuit.

[0116] When the six-way valve 610 is in the second state, the carrier gas enters the third valve of the six-way valve 610 from the third carrier gas inlet 650, enters the fourth valve from the third valve, enters the carrier gas circuit 640 from the fourth valve, enters the second valve from the carrier gas circuit 640, enters the first valve from the second valve, and is introduced into the third chromatographic column 620 and the first channel 300 from the first valve, so as to realize pushing the sample gas after the SF6 peak out of the third chromatographic column 620 into the first channel 300, avoiding residue, and further avoiding the corrosion of the chromatographic column by the SF6 decomposition products.

[0117] As Figure 1 shown, the chromatographic column selected for the first chromatographic column 200 is a Q column; the chromatographic columns selected for the second chromatographic column 400 are a Q column and a CPCIL5 column; the chromatographic column selected for the third chromatographic column 620 is a 5A molecular sieve.

[0118] In this technical solution, the first chromatographic column 200 uses a Q column, the second chromatographic column 400 selects a Q column and a CPCIL5 column, and the third chromatographic column 620 selects a 5A molecular sieve.

[0119] Previously, the chromatographic column used in single-channel detection was a 5A molecular sieve. This chromatographic column had better detection effects on the discharge decomposition products before the SF6 peak in the SF6 / N2 mixed gas. However, it was easily corroded by the SF6 decomposition products. When the 5A molecular sieve was corroded, the detection effect would decline. Therefore, the present invention defines three types of chromatographic columns in the gas chromatography-mass spectrometry instrument. Among them, the Q column and the CPCIL5 column can resist high corrosion. Therefore, the first chromatographic column 200 uses the Q column to separate the discharge decomposition products of the mixed gas before the SF6 peak. At the same time, the discharge decomposition products of the mixed gas after the SF6 peak still pass through the first chromatographic column 200. The second chromatographic column 400 uses the Q column and the CPCIL5 column, mainly for separating the discharge decomposition products of the mixed gas after the SF6 peak. The third chromatographic column 620 still uses the 5A molecular sieve, mainly for further separating the discharge decomposition products of the mixed gas before the SF6 peak. At the same time, the discharge decomposition products of the mixed gas after the SF6 peak do not pass through the third chromatographic column 620, and the shunt component 600 is used to prevent the SF6 decomposition products from corroding the third chromatographic column 620.

[0120] This setting further prevents the sample gas from corroding the chromatographic column, thereby improving the accuracy of the detection results.

[0121] As Figure 2 shown, according to the second aspect of the embodiments of the present application, a method for detecting discharge decomposition products of a mixed gas is proposed, which is applied to the gas chromatography-mass spectrometry instrument described in any one of the above, and includes:

[0122] Step 101: Introduce the discharge decomposition products of the SF6 / N2 mixed gas into the sample metering assembly 100. When no detection signal is sent to the sample metering assembly 100, the ten-way valve 110 in the sample metering assembly 100 is in the first state, and the discharge decomposition products of the SF6 / N2 mixed gas are directly discharged after entering the sample metering assembly 100.

[0123] Step 102: Send a detection signal to the sample metering assembly 100, and the ten-way valve 110 in the sample metering assembly 100 switches from the first state to the second state.

[0124] Step 103: The sample metering assembly 100 introduces the discharge decomposition products of the SF6 / N2 mixed gas into the first chromatographic column 200 and the second chromatographic column 400.

[0125] Step 104: The discharge decomposition products of the SF6 / N2 mixed gas enter the first channel 300 through the first chromatographic column 200, and the first channel 300 detects the substances in the mixed gas before the SF6 peak time.

[0126] Step 105: The decomposition products of the SF6 / N2 mixed gas enter the second channel 500 through the second chromatographic column 400, and the second channel 500 detects the substances after the peak emergence time of SF6 in the mixed gas.

[0127] In this technical solution, the present invention first proposes to transform the gas chromatography-mass spectrometry (GC-MS) by using a dual-channel injection method. The dual-channel injection method can separate sulfides and inorganic substances into different channels through the separation of the chromatographic column, and the detection results are reflected on the first channel 300 (BID channel) and the second channel 500 (MSD channel) respectively. It avoids the situation where peaks such as nitrogen, oxygen, and methane are all included in nitrogen during single-channel detection before, and uses multiple chromatographic columns to separate the samples, so that the detection results will not show peak emergence crossover, overlap, etc., and the detection efficiency is higher.

[0128] As Figures 3 - 9 shown, use the transformed gas chromatography-mass spectrometry and apply the adaptation setting method to qualitatively and quantitatively calibrate the existing standard gas to verify whether the instrument can have obvious peak emergence for the measured samples after transformation, and there is no overlapping phenomenon, and the samples can be accurately qualitatively determined. The gases contained in the standard gas measured in the present invention are Standard Gas 1: oxygen (O2), nitrogen (N2), hydrogen (H2), methane (CH4), carbon tetrafluoride (CF4), carbon monoxide (CO), carbon dioxide (CO2), hexafluoroethane (C2F6), nitrous oxide (N2O), octafluoropropane (C3F8), nitrogen trifluoride (NF3). Standard Gas 2: hydrogen sulfide (H2S), sulfuryl fluoride (SO2F2), carbon disulfide (CS2), sulfuryl fluoride (SOF2), carbonyl sulfide (COS). Standard Gas 3: hexafluoropropene (C3F6), octafluorocyclobutane (C4F8), trifluoromethane (CHF3), pentafluoroethane (C2HF5), heptafluoropropane (C3HF7), trifluoroethane (C2H3F3), tetrafluoroethane (C2H2F4), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6). The detection results of the above standard gases using the transformed instrument are as shown above Figures 3 - 9 shown.

[0129] It can be seen from the above detection results of the standard gas that the transformed gas chromatography-mass spectrometry can separate the standard gas, and the peak emergence is obvious, without the peak emergence overlap, crossover, etc. that existed before the transformation, and all components have obvious peak emergence. The transformed instrument can qualitatively and quantitatively analyze the decomposition products after the discharge decomposition of the SF6 / N2 mixed gas, and the research results are helpful for on-site equipment operation and maintenance and diagnosis.

[0130] The described method for detecting the decomposition products of the mixed gas discharge further includes: a splitting component is arranged between the first chromatographic column and the first channel, and the splitting component is used to introduce the sample gas into the first channel or discharge it from the gas chromatography-mass spectrometry instrument; when SF6 in the sample gas has not reached the peak position, the splitting component introduces the sample gas into the first channel; after SF6 in the sample gas reaches the peak position, an electrical signal is sent to the splitting component, and the splitting component discharges the sample gas from the gas chromatography-mass spectrometry instrument.

[0131] In this technical solution, a splitting component is added between the first chromatographic column and the first channel, and through valve switching operation, the highly corrosive decomposition products of SF6 are prevented from corroding the third chromatographic column.

[0132] In the present invention, the terms "first", "second", and "third" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance; the term "plurality" refers to two or more, unless otherwise clearly defined. Terms such as "installed", "connected", "connected to", and "fixed" should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral connection; "connected" can be a direct connection or an indirect connection through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0133] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the terms "upper", "lower", "left", "right", "front", "rear", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or unit referred to must have a specific direction, be constructed and operated in a specific orientation, and therefore, should not be construed as a limitation of the present invention.

[0134] In the description of this specification, the description of terms such as "one embodiment", "some embodiments", "specific embodiments", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or instance. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0135] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A chromatography-mass spectrometry instrument, characterized in that: include: A sample quantitative component, which is used to quantitatively control the sample gas and divide the sample gas into two paths; a first chromatographic column, the first chromatographic column being connected to the sample quantification component; A first channel, the first channel is connected to the first chromatographic column, the first channel is a dielectric barrier discharge plasma detector channel, and the first channel is used to detect substances before the peak time of the sample gas SF6; a second chromatographic column, the second chromatographic column being connected to the sample quantification component; A second channel, the second channel is connected to the second chromatographic column, the second channel is a mass spectrometer detector channel, and the second channel is used to detect substances after the peak time of the sample gas SF6; A flow splitter component, which is disposed between the first chromatographic column and the first channel, and which introduces the sample gas into the first channel before the SF6 in the sample gas reaches the peak time, and which discharges the sample gas after the SF6 in the sample gas reaches the peak time; The flow splitting component comprises a six-way valve, a third chromatographic column and an exhaust port, the six-way valve has a first state and a second state, the third chromatographic column is connected to valve No. 1 of the six-way valve, the third chromatographic column is connected to the second channel, and the exhaust port is connected to valve No. 5 of the six-way valve; When the six-way valve is in the first state, valve No. 2 inside the six-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, and valve No. 6 is connected to valve No. 1; When the six-way valve is in the second state, valve No. 1 inside the six-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 6 is connected to valve No. 1, valve No. 6 of the six-way valve is connected to the first chromatographic column, and valve No. 1 of the six-way valve is connected to the first channel.

2. The chromatography-mass spectrometry instrument according to claim 1, characterized in that: The sample quantification component comprises: A ten-way valve, the ten-way valve having a first state and a second state, the ten-way valve being connected to the first chromatographic column and the second chromatographic column; A sample air inlet pipeline, wherein the sample air inlet pipeline is connected to the ten-way valve; A sample exhaust pipeline, wherein the sample exhaust pipeline is connected to the ten-way valve; a first quantitative ring, wherein the first quantitative ring is connected to the ten-way valve; a second quantitative ring, the second quantitative ring being connected to the ten-way valve; a first carrier gas inlet, the first carrier gas inlet being connected to the ten-way valve; A second carrier gas inlet is connected to the ten-way valve.

3. The chromatography-mass spectrometry instrument according to claim 2, characterized in that: When the ten-way valve is in the first state, valve No. 2 inside the ten-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, valve No. 6 is connected to valve No. 7, valve No. 8 is connected to valve No. 9, and valve No. 10 is connected to valve No. 1; When the ten-way valve is in the second state, valve No. 1 in the ten-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 5 is connected to valve No. 6, valve No. 7 is connected to valve No. 8, and valve No. 9 is connected to valve No. 10; The sample air inlet pipeline is connected to the No. 2 valve of the ten-way valve; The sample exhaust pipeline is connected to valve No. 1 of the ten-way valve; One end of the first quantitative ring is connected to the seventh valve of the ten-way valve, and the other end of the first quantitative ring is connected to the tenth valve of the ten-way valve; One end of the second quantitative ring is connected to the No. 3 valve of the ten-way valve, and the other end of the second quantitative ring is connected to the No. 6 valve of the ten-way valve; The first chromatographic column is connected to valve No. 8 of the ten-way valve, and the second chromatographic column is connected to valve No. 4 of the ten-way valve; The first carrier gas inlet is connected to the ninth valve of the ten-way valve; The second carrier gas inlet is connected to valve No. 5 of the ten-way valve.

4. The chromatography-mass spectrometry instrument according to claim 2, characterized in that: The sample quantification component also includes: A shunt flow path is provided between the sample quantification component and the second chromatographic column.

5. The chromatography-mass spectrometry instrument according to claim 4, characterized in that: The diversion component also includes: A carrier gas circuit, one end of which is connected to valve No. 2 of the six-way valve, and the other end of which is connected to valve No. 4 of the six-way valve; A third carrier gas inlet is connected to valve No. 3 of the six-way valve.

6. The chromatography-mass spectrometry instrument according to claim 5, characterized in that: The chromatographic column selected for the first chromatographic column is a Q column; The chromatographic columns selected for the second chromatographic column are Q column and CPCIL5 column; The chromatographic column selected for the third chromatographic column is 5A molecular sieve.

7. A method for detecting mixed gas discharge decomposition products, characterized in that: The chromatographic mass spectrometer used in any one of claims 1 to 6 comprises: When the discharge decomposition products of the SF6 / N2 mixed gas are introduced into the sample quantitative component and no detection signal is sent to the sample quantitative component, the ten-way valve in the sample quantitative component is in the first state, and the discharge decomposition products of the SF6 / N2 mixed gas are directly discharged after being introduced into the sample quantitative component; Sending a detection signal to the sample quantification component, the ten-way valve in the sample quantification component switches from a first state to a second state; The sample quantitative component introduces discharge decomposition products of the SF6 / N2 mixed gas into the first chromatographic column and the second chromatographic column; The discharge decomposition products of the SF6 / N2 mixed gas enter the first channel through the first chromatographic column, and the first channel detects the substances before the SF6 peak time in the decomposition products; The discharge decomposition products of the SF6 / N2 mixed gas enter the second channel through the second chromatographic column, and the second channel detects substances after the SF6 peak time in the decomposition products.

8. The method for detecting mixed gas discharge decomposition products according to claim 7, characterized in that: Also includes: A flow splitter assembly is provided between the first chromatographic column and the first channel, and the flow splitter assembly is used to introduce the sample gas into the first channel or discharge the chromatograph-mass spectrometer; When SF6 in the decomposition products has not reached the peak position, the flow splitting component introduces the sample gas into the first channel; After SF6 in the decomposition product reaches the peak position, an electrical signal is sent to the diversion component, and the diversion component discharges the sample gas out of the chromatography-mass spectrometry instrument.

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